Basic mixtures of metal salts and lubricants containing them



United States Patent 3,232,883 BASIC MIXTURES 0F METAL SALTS ANZ) LUBRICANTS CONTAINING THEM William M. Le Suer, Cleveland, ()hio, assignor to The Lubrizol Corporation, Wickliffe, Ohio, a corporation of Ohio N0 Drawing. Filed Dec. 28, 1961, Ser. No. 162,956 11 Claims. (Cl. 252-325) This invention relates to metal salts of organic phosphorus acids and in a more particular sense to mixtures of at least two alkaline earth metal salts of oil-soluble phosphorus acids. Such mixtures are suitable for use as additives in hydrocarbon oil compositions such as fuel oils, gasolines, greases, and fluid lubricants.

Hydrocarbon oils are prone to degradation in service. A substantial portion of the degradation products consists of acidic substances which are corrosive to metals and tend to form sludge-like and varnish-like deposits. To inhibit such degradation and to minimize the harmful effects of the degradation products, it is a common practice to incorporate into the hydrocarbon oil one or more chemical additives. Metal salts of oil-soluble organic acids, e.g., phosphorus acids, are useful as such additives. The basic metal salts, i.e., those in which the metal is present in a stoichiometrically greater amount than the organic acid radical, are especially efiective because of their ability to neutralize the acidic degradation products. In general, it is recognized also that the higher the basicity of the metal salt, the greater its capacity to counteract the undesirable acidic products, and the greater its effectiveness as an oil additive.

Accordingly it is a principal object of this invention to provide additives for use in hydrocarbon oils.

It is also an object of this invention to provide hydrocarbon oil concentrates of such additives.

It is also an object of this invention to provide hydrocarbon oil compositions.

It is further an object of this invention to provide lubricating compositions.

These and other objects are attained in accordance with this invention by providing a basic mixture of alkaline earth metal salts of acidic phosphorized substantially aliphatic hydrocarbons, said mixture being characterized by a metal ratio greater than about 2.5 and comprising (A) from 40 parts to 95 parts by weight of a said metal salt having a metal ratio greater than 4 and (B) from parts to 60 parts by weight of a said metal salt having a metal ratio less than 2.

The metal ratio of a metal salt designates the ratio of the total chemical equivalents of the metal to the chemical equivalents of the metal which is in the form of the normal salt (i.e., the neutral salt) of the organic acid. To illustrate, a metal salt containing 5 equivalents of the metal per equivalent of the organic acid radical has a metal ratio of 5, and a neutral metal salt has a metal ratio of 1.0. It will be noted that the metal ratio of a mixture of two or more metal salts is the average value based upon the metal ratios and the relative proportions of the individual component metal salts in the mixture.

A principal significance of the above basic mixture of this invention is its unusual effectiveness as an oil additive to inhibit degradation of hydrocarbon oils and to combat the harmful effects of the oil degradation products. This effectiveness is associated with several critical aspects of this invention, namely, that the mixture contain at least one relatively highly basic metal salt characterized by a metal ratio greater than 4 and at least one neutral metal salt or a relatively less basic metal salt characterized by a metal ratio of less than 2, that the reltive proportions of these two types of metal salts be within the above stated range, and that the mixture itself be char- 3,232,383 Patented Feb. 1, 1966 acterized by a metal ratio of at least about 2.5, preferably from about 3 to about 7.

The relatively highly basic metal salt of the mixture preferably has a metal ratio greater than about 5 or 6 and may have a metal ratio of about 10 or higher. The relatively less basic metal salt of the mixture may have a metal ratio of about 1, 1.5, or up to about 2.

As indicated previously, the metal salts are derived from acidic phosphorized substantially aliphatic hydrocarbons. Such hydrocarbons include, for example, the white oils and other liquid petroleum oils having at least about twelve carbon atoms and include also synthetic hydrocarbons such as are obtained by the reduction of fatty oils.

A convenient source of the substantially aliphatic hydrocarbons are the olefin polymers having molecular Weights of at least about 150 and up to about 48,000 preferably from about 500 to about 5000. The polymers include the homopolymers and the interpolymers of monoolefins having from two to twelve carbon atoms, e.g., ethylene, propene, l-butene, isobutene, l-hexene, l-octene, Z-methyl-l-heptene, 3-cyclohexyl-l-butene, l-decane, 2- methyl-S-propyl-l-hexene, etc.

Also useful are the interpolymers of such mono-olefins with other interpolymerizable olefinic substances such as aromatic olefins, cycloaliphatic olefins, and polyolefins. The interpolymers, include, for example, those prepared by polymerizing isobutene with styrene; isobutene with butadiene; propene with isoprene; ethylene with piperylene; isobutene with chloroprene; isobutene with p-methyl styrene; l-hexene with 1,3-hexadiene; isobutene with styrene and piperylene; etc.

The relative proportions of the mono-olefins to the other olefinic monomers in the interpolymers may vary within wide ranges provided that the polyolefin, if used, is not present in sufficiently high proportions as to cause substantial cross-linking and insolubility. Specific examples of the useful interpolymers include the copolymer of 95 (by weight) of isobuene with 5% of styrene; the terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; the terpolymer of 95% of isobutene with 2% of l-butene and 3% of l-hexene; the terpolymer of 60% of isobutene with 20% of l-pentene and 20% of l-octene; the copolymer of of l-hexene and 20% of l-heptene; the terpolymer of ofisobutene with 2% of cyclohexene and 8% of propene; and the copolymer of 80% of ethylene and 20% of propene.

Methods of preparing the polymers and the interpolymers illustrated above are known. A particularly useful method comprises the treatment of an olefin (e.g., isobutene) at a temperature from about -60 C. to about 20 C. with a Friedel-Crafts catalyst, e.g., boron trifluoride. The use of a solvent to facilitate mixing and transfer of the heat of reaction is advantageous. Such solvents include n-butane, isobutane, n-hexane, naphtha, carbon tetrachloride, and ethane.

The olefin polymers may be phosphorized by treatment with a phosphorus sulfide such as phosphorus pentasulfide, phosphorus sesquisulfide, phosphorus heptasulfide, or phosphorus thiochloride. Other useful phosphorizing agents are exemplified by phosphorus thiobromide, chlorine and phosphorus trichloride, phosphorus trichloride and sulfur, yellow phosphorus and sulfur monochloride, yellow phosphorus and sulfur, phosphorus oxychloride, phosphorus trichloride, phosphorus tribromide, and yellow phosphorus and sulfur dichloride.

Various techniques to effect the phosphorization are known. A very commonly used method involves simply mixing the olefin polymer with the phosphorizing agent at the desired temperature, usually above 80 C. and preferably between C. and 300 C. Another method consists of chlorinating the olefin polymer and reactphenol, amine, or thiol.

1 ing the chlorinated polymer with a phosphorizing agent.

The amount of the phosphorizing agent to be used in the treatment of an olefin polymer depends upon the na ture of the product desired. For most applications, products having aphosphorus content from 0.05% to 10%,

more often from 0.1% to 5%, are desirable. Thus, the relative proportion of the phosphorizing agent to be used is such as to provide from about 0.05 to parts (by weight), more often from 0.1 to 5 parts, of phosphorus per 100 parts of the olefin polymer in the reaction mixture. In most instances, from 0.1 part to 50 parts of a phosphorizing agent is used per 100 parts of the olefin polymer.

The phosphorized olefin polymers are acidic composil tions, susceptible to neutralization with a basic metal reagent to form a metal salt.

A preferred method for preparing the metal salt, however, involves first hydrolyzing the phosphorized olefin polymer by treatment with water or steam and then neutralizing the hydrolyzed intermediate with the basic metal reagent. The hydrolysis removes from the phosphorized olefin polymer that portion of the A phosphorus which is loosely held and results in a product of light color and high stability. The temperature at ;which the hydrolysis is carried out is preferably between 100 C. and 200 0., although it can be 80 C., or even compounds are preferred.

A convenient method for preparing the basic salts involves mixing the phosphorized olefin polymer with an excess (e.g., two to three times the stoichiornetric amount) of an alkaline earth metal base or preparing such a mixture and subsequently treating the mixture with carbon dioxide. The incorporation of a still larger excess of a metal base is usually facilitated by the use in the neutralization mixture of a promoting agent which in most instances is an active hydrogen compound, i.e., an alcohol,

Specific examples of such promoting agents are methanol, propanol, cyclohexanol, octanol, dodecanol, behenyl alcohol, benzyl alcohol, phenol, naphthol, didodecylphenol, condensation product of octylphenol and formaldehyde, aniline, toluidine, phenothiazine, phenylene diamine, cyclohexylamine, octylamine, dimethylamine, methyl mercaptan, thiophenol, and tert-octyl mercaptan. The neutralization and the carbonation steps are carried out at temperatures between room temperature and 300 C.

To illustrate, the preparation of a highly basic metal salt can be effected by carbonating (preferably at 100- 300 C.) a mixture of a phosphorized olefin polymer, a phenolic compound such as p-octylphenol, and a large excess of a metal base such as barium oxide or barium hydroxide until a substantial portion of the metal base is converted to the carbonate. In the case of an alcohol being present as the promoting agent, the carbonation temperature is within the range from about 25 C. to the boiling point of the alcohol.

The methods for phosphorizing olefin polymers as well as for preparing the metal salts of phosphorized olefin polymers are known in the art, e.g., US. Patents 2,316,- 078, 2,316,079, 2,316,085, 2,616,904, 2,616,905, 2,616; 906, 2,616,911, 2,616,924, 2,616,915, 2,950,378, and 2,938,894; and co-pending applications Ser. No. 809,523, filed April 29, 1959 now abandoned; Ser. No. 838,024, filed September 4, 1959 now US. Patent No. 3,033,890; Ser. No. 30,477, filed May 20, 1960 now US. Patent No. 3,089,867; and Ser. No. 10,104, filed February 23, 1960 now US. Patent No. 3,049,531.

' The following examples illustrate the alkaline earth metal salts of this invention and the methods by which they are prepared. The neutralization number of the metal salts is determined according to ASTM Test procedure D974-487. The reflux base number is a mcasurement of the basicity of the metal salts. It is determined by the following procedure: A sample (l-1.2 grams) of the metal salt is dissolved in 25 cc. of a solvent mixture consisting of benzene and isopropanol in equal Weight proportions and a trace of Water. The solution is mixed with an excess and known quantity of a standardized hydrochloric solution of 0.1N and the mixture refluxed for 30 minutes. The residual acidity of the mixture is then determined by titration with a standardizedpotassium hydroxide solution according to ASTM Test procedure No. D66458. The basicity of the metal salt is indicated by the quantity of the hydrochloric acid consumed in the process.

EXAMPLE 1 To a refluxing (99 C.) mixture of 1000 parts (by weight) of a chlorinated polyisobutene having a molecular weight of 1000 and a chlorine content of 4.3%, and 61 parts of heptylphenol, there is added parts of phosphorus trichloride. The mixture is heated until the reflux temperature reaches 200 C. (in 4 hours). To this mixture there is added 110 parts of phosphorus trichloride and the resulting mixture is heated at 200 C. for 6.5 hours, and then blown with nitrogen at 180 200 C. for 2 hours. The phosphorized polymer thus obtained is hydrolyzed by treatment with steam at 150 160 C. for 3 hours. The hydrolyzed product has a phosphorus content of 2.2% and a chlorine content of 0.3%. A basic barium salt is prepared by carbonating a mixture of 270 parts of a mineral oil, 18 parts of water, 143 parts of the above hydrolyzed acid, 38 parts of heptylphenol, and parts of barium oxide at 130140 C. until the mixture is substantially neutral to phenolphthalein. The mixture is then dried by blowing it with nitrogen at 155 C. and diluted with mineral oil to an oil solution having a barium sulfate ash of 25%. The final solution is found to contain 0.41% of phosphorus, a neutralization number less than 5 (basic), a reflux base number of 107, and a 0 metal ratio of 8.3.

EXAMPLE 2 A mixture of 1000 parts (by weight) of a polyisobutene having a molecular weight of 1000 and 90 parts of phosphorus pentasulfide is prepared at room temperature, heated to 260 C. in 5 hours, and maintained at this temperature for 5 hours. It is then cooled to 150 C. and hydrolyzed by treatment with steam at this temperature for 5 hours. The hydrolyzed acid has a phosphorus content of 2.4% and a sulfur content of 2.8%. In a separate vessel a mixture of oil and barium hydroxide is prepared by mixing 2200 parts of a mineral oil and 1150 parts of barium oxide at 88 C. and blowing the mixture with steam for 3 hours at 150 C. To this mixture there is added, portionwise, throughout a period of 3 hours, 1060 parts of the above hydrolyzed acid at 145-150 C., and then 360 parts of heptylphenol in 1.5 hours. The resulting mixture is blown with carbon dioxide at a rate of 100 pounds per hour for 3 hours at 157 C. The carbonated product is mixed with 850 parts of a mineralo-il and dried by blowing it with nitrogen and 150 C. The dried product is filtered and the filtrate is diluted with mineral oil to a solution having a barium sulfate ash content of 25%. The final solution is found to have a phosphorus content of 0.38%, a sulfur content of 0.48%, a neutralization number less than 5 (basic), a reflux base number of 109, and a metal ratio of 7.2.

EXAMPLE 3 A hydrolyzed, acidic phosphorized polyisobutene is prepared by the procedure of Example 1 except that the amount of heptylphenol used in the preparation of the phosphorized polymer is 30 parts (by Weight) per 1000 parts of the chlorinated polyisobutene. A basic barium salt is prepared by mixing 240 parts of a mineral oil, 24

parts of water, 168 parts of the hydrolyzed acid, 44 parts of heptylphenol, and 275 parts of barium oxide at 88- 120C., blowing the mixture with steam at 135 C., and carbonating the mixture at 132-140 C. for 21 hours until the mixture is substantially neutral to phenolphthalein. The mixture is then diluted with 83 parts of mineral oil, dried by blowing it with nitrogen at 150 C. for 2 hours and then filtered. The filtrate is diluted further with mineraloil to a solution having a barium sulfate ash -content of 38.5%. The final solution is found to contain 1 also a phosphorus content of 0.4%, a neutralization number less than5 (basic), a reflux base number of 173, and a metal ratio of 12.8. i

EXAMPLE 4 A polyisobutene having a molecular weight of 48,000 is phosphosulfurized by mixing 123 parts (by Weight) of a 38% mineral oil solution of the polymer with 2.8 parts of phosphorus pentasulfide at 94 C. and heating the mixture to 260 C..in 6 hours and then at 260 C. for 2 additional hours. The product is hydrolyzed with steam at 150 C. to give an acid having a phosphorus content of 0.64% and a sulfur content of 0.48%. A basic barium salt of the acid is prepared by carbonating at 150 C. a mixture of 1000 parts of the acid, 79 parts of heptylphenol, parts of water, and 224 parts of barium oxide until the mixture is substantially neutral to phenolphthalein. The carbonating mixture is diluted with 400 parts I of mineral oil, 50 parts of isooctyl alcohol, and 500 parts of benzene, filtered, and the filtrate is heated to 150 C./ 30 mm. to distill off the volatile components. The residue is found to have a barium sulfate ash content of 18.2%, a phosphorus content of 0.14%, a neutralization number of 1.5 (acid), a reflux base number of 76.5, a sulfur content of 0.2%, and a metal ratio of 7.6.

EXAMPLE 5 A barium salt is obtained by mixing 2000 parts (by Weight) of the hydrolyzed acid of Example 1, 500 parts of mineral oil, 100 parts of water, and 163 parts of barium oxide, heating the mixture at 150 C. for 2 hours, and filtering the mixture. The filtrate is found to have a barium sulfate ash content of 10.1%, a phosphorus content of 1.9%, and a metal ratio of 1.04.

EXAMPLE 6 A polyisobutene having a molecular weight of 1000 is phosphosulfurized by heating 100 parts of the polyisobutenewith 9 parts of phosphorus pentasulfide at 260 C. for 5 hours. The phosphosulfurized polymer is hydrolyzed by treatment with steam at 155 C. to produce an acid having a phosphorus content of.2.3%, a sulfur content of 2.7% and an acid number of 48. A slightly basic barium salt of the hydrolyzed acid is prepared by mixing 2330 parts of the acidwith 185 parts of barium oxide and 100 parts of water and 700 parts of mineral oil at 70 C. and heating the mixture at the reflux temperature for 1 hour and then drying the mixture at 150 C. for 2 hours. The mixture is then filtered and the filtrate has a barium sulfate ash content of 9.3%, a phosphorus con tent of 1.7%, a sulfur content of 1.8%, and a metal ratio of 1.3.

EXAMPLE 7 A neutral barium salt is obtained by reacting at 130- 135 C. stoichiometric amounts of the hydrolyzed acid of Example 4, water, and barium oxide in the presence of mineral oil. The product is diluted further with mineral oil to give an oil solution having an oil content of 85%. The solution is found to have a barium content of 0.94%, a phosphorus content of 0.3%, and a sulfur content of 0.34%.

EXAMPLE 8 A polyisobutene having a molecular weight of 1000 is phosphosulfurized by heating a mixture of 750 parts of the polyisobutene with 110 parts of phosphorus pentasuL 150 C. for 1 hour and filtering the mixture. The filtrate is found to have a barium sulfate ash content of 11.6%, a phosphorus content of 2%, a sulfur content of 0.8%, and a metal ratio of 1.

EXAMPLE 9 A neutral barium salt is prepared by the reaction of stoichiometric amounts of barium hydroxide and thehydrolyzed acid of Example 8 (Without air blowing) and the reaction production is diluted with mineral oil to a solution having a barium sulfate ash content of 9.3%, a phosphorus content of 2.1% and a sulfur content of 1%.

EXAMPLE 10 A basic barium salt is prepared from the hydrolyzed acid of Example 8 (without airblowing) and diluted with mineral oil to a solution having a barium sulfate ash content of 14%, a phosphorus content of 1.5%, a sulfur content of 1.3%, and a metal ratio of 2.

EXAMPLE 11 A neutral barium salt is prepared from the hydrolyzed acid of Example 8 (without air blowing) and diluted with mineral oil to a solution having a barium sulfate ash con tent of 6.9%, a phosphorus content of 1.3%, and a sulfur content of 1.1%.

As indicated previously, the relative proportions of the two types of metal salts in the basic mixtures of this invention are of critical importance to the effectiveness of such mixtures as additives in oils. The ratio of the metal salt (A), i.e., the highly basic metal salt, to the metal salt (B), i.e., the slightly basic or neutral metal salt, should be at least about :60 (by weight). The preferred ratio of (A) :(B) is withinthe range from :50 to 70:30, respectively such as 60:40. Onthe other hand, mixtures in which the ratio of (A) (B) is 80:20 or 90:10 or, as high as 95:5 have been found to be equally effective. This ratio, i.e., 95:5, appears to represent a practical upper limit of the relative amounts of the two types of metal salts..

It will be noted further that another critical feature of this invention is that the basic mixture must be characterized by a metal ratio of at least about 2.5. Thus, for a mixture having a particular metal ratio, less of a highly basic (A) is required than of a less basic (A). To illustrate, a basic mixture containing 50 parts of a highly basic salt having a metal ratio of 10 and 50 parts of a neutral metal salt has a resultant metal ratio of 5.5; another basic mixture containing 70 parts of a highly basic metal salt having a metal ratio of 7.4 and 30 parts of a neutral metal salt likewise has a resultant metal ratio of 5.5.

The concentration of the basic mixtures of this invention as additives in oils may vary within wide ranges, depending upon the type of the oils and the nature of the service to Which ;the oils are to be subjected. The optimum concentrations usually range from about 0.001% to about 20% by weight. To illustrate, lubricants for use in gasoline internal combustion engines may contain from 1about0.5% to about 10% of the additive, lubricants for use in gears and diesel engines may contain more than 10% of the additive, and hydrocarbon fuels may contain as little as 0.01% or even less of the additive. For instance, a lubricating composition may comprise from about 99 to about parts by weight of a mineral lubricating oil and from about 1 to about .20 parts by Weight of the basic mixture.

The lubricating oils in which the compositions of this invention are useful as additives may be of synthetic, animal, vegetable, or mineral origin. Ordinarily mineral 7 lubricating oils are preferred by reason of their availability, general excellence, and low cost. For certain applications, oils belonging to one of the other three groups may be preferred. For instance, synthetic polyhibitors, load-carrying additive-s, anti-foam additives, pour point depressants, viscosity index improving agents, additives to improve the frictional characteristics, etc.

The ashless detergents include the neutralization prodester oils such as didodecyl adipate and di-2-ethylhexyl 5 nets of an alkenyl-substituted succinic anhydride having sebacate are often preferred as jet engine lubricants. 50 or more carbon atoms in the alkenyl-substituent with Normally the lubricating oils preferred will be fluid oils, an amine, preferably an alkylene amine such as ethylene ranging in viscosity from about 40 Saybol't Universal diamine, diethylene triamine, tetraethylene pent-amine, Seconds at 100 F. to about 200 Saybolt Universal Secpentaethylene hexamine, hexamethylene diamine, dionds at 210 F. triethylene diamine, piperazine, or aminoethyl morpho- To prepare the oil compositions containing the basic line; the copolymer of a long chain alkyl (e.g., dodecyl) mixtures of this invention, the two types of metal salts acrylate or methacrylate with from 2% to 10% (by 'may be added separately to the oil or they may be Weight) of a polar-substituted acrylate or methacrylate mixed first and the resulting mixture added to the oil. (e.g., beta-diethylaminoethyl acrylate). A convenient method is'to prepare a concentrate of the The metal-containing detergents may be normal or the mixture by dissolving the mixture in a limited amount of basic alkali metal salts or alkaline earth metal salts of the oil and then diluting the concentrate with additional oil soluble sulfonic acids such as petroleum sulfonic acids amounts of the oil to prepare the final oil composition. or sulfonic acids obtained by the sul'fonation of an The unusual effectiveness of the basic mixtures of the alkyla-ted aromatic compound (e.g., didodecyl benzene). metal salts of this invention as additives in oils to inhibit Oxidation inhibitors include, for example, hindered the formation of harmful deposits is shown by the rephenols, such as 2,6-ditert-butyl-4-methylphenol, 2,2',6, sults (Table I) of a deposit-inhibition test. In this test 6 tetra tert butyl 4,4 methylene bisphenol, a 350-cc. sample of a lubricating oil containing the and Z-tert-pentyl-6-isohexylphenol; metal phenates such additive is placed in a 2" x 15" borosilicate tube. A as barium octylphenate, calcium didodecylphenate, stronsteel panel is immersed in the oil. The sample is heated tium salt of the product obtained by the condensation of at 300 F. for 96 hours while air is bubbled through the a 2:1 molar mixture of heptylphenol and formaldeoil at the rate of 10 liters per hour. The oxidized sample hyde, barium salt of bis(hydroxyphenyl)sulfide, and calis cooled to 120 F., mixed with 0.5% of water, homogcium salt of the product obtained by the condensation of enized, allowed to stand at room temperature for 24 a 2:1 molar mixture of heptylphenol and formaldehours, and then filtered through two layers of No. 1 such as phenylene diamine, N,N-dibutyl phenylene diwhatman filter paper at 20 mm. mercury pressure. The amine, naphthyl amine, N-beta-phenyl naphthylamine, weight of the precipitate, washed with naphtha and dried, o-aminobenzoic acid, p-aminobenzoic acid, methyl ester is taken as a measure of the eiiectiveness of the additive, of o-aminobenzoic acid, and diphenylamine; carbam-ates i.e., the greater the weight of the precipitate the less and xanthates such as methyl N-octylcarbamate, dodecyl eifective the additive. The lubricating oil used in the N-phenyldithiocarbamate, and cyclohexy-l N,N'-dibutyltest is a Mid-Continent conventional-1y refined petroleum carbamate. oil having a viscosity of about 200 SUS at 100 F. Load-carrying additives include, e.g., chlorinated par- The basic mixtures of this invention are suitable for afiin oils containing from 20% to 70% of chlorine, use in oil compositions containing other additives such chlorinated eicosane wax containing from to of as ashless detergents, supplemental metal-containing de- 0 chlorine, hexachlorodiphenyl ether, polychloro-diphenyl, tergents, corosion inhibitors, rust inhibitors, oxidation inetc. Additives to improve the frictional characteristics Table 1 Metal salt(s) in the lubricant Weight ratio Resulting Test result Lubricant tested A. Salt having metal ratio greater B. Salt having metal ratio less of AzB in metal ratio (mg. of sludge (*Denotes baseline) than 4 than 2 mixture of mixture per ml. of

lubricant) Identity Metal Ratio Identity Metal Ratio 900 100 60 Example 3. 220 Example 4. 88 None l 635 1.3 805 1 600 1 700 2 1 220 1 300 8.3 1 7.6 19 8.3 1 6.1 9 8.3 do 1 4.7 s 7.2 ExampleG 1.3 6.6 5 7.2 do 1.3 5.4 5 7.2 1.3 4.3 4 12.8 1 11.6 19 12.8 1 9.3 3 12.8 1 6.9 4 7.6 1 6.9 47 7.6 1 5.6 70 7.6 1 4.3 66 12.8 Examples l 6.9 15 12.8 Example 6 1.3 5.9 20 12.8 Example 9.-. 1 3.4 250 12.8 do. 1 8.9 19 12.8 do 1 10.4 34 12.8 do 1 12.1 32 8.3 Example 11 1 4.7 4 8.3 do 1 6.1 5 8.3 do 1 7.6 10 12.8 Example 10 2 7. 1 3 12.8 -416 2 9.6 12 12.8 1o 2 11.7 34

are illustrated by methyl oleate, oleic acid, stearic acid, s'uliurized sperm oil, sperm oil, corn oil, mono-stearyl ester of glycerol, and quionid-ine dioleate. Pour point depressing agents are, e.g., wax-alkylated naphthylenes, copolymers of butyl methacrylate with decyl methacry-late, etc.

The iollowing examples illustrate the oil compositions containing the basic mixtures of this invention. (All parts are by weight.)

COMPOSITION A (LUBRICANT) Parts SAE 10W30 mineral oil 90 Basic salt of Example 1 8 Neutral salt of Example 5 2 COMPOSITION B (FUEL OIL) Catalytically cracked No. 2 light petroleum fuel oil 99 Basic salt of Example 1 0.5 Neutral salt of Example 6 0.5

COMPOSITION C (LUBRICANT) SAE 30 mineral oil 85 Basic salt of Example 4 10 Slightly basic salt of Example 10 5 COMPOSITION D (LUBRICANT CONCENTRATE) SAE 20 mineral oil 50 Basic salt of Example 3 30 Neutral salt of Example 9 20 COMPOSITION E (LUBRICANT CONCENTRATE) SAE 10lW30 mineral oil 20 Basic salt of Example 3 60 Neutral salt of Example 11 30 Zinc dioctylphosphorodithioate 20 COMPOSITION F (LUBRICANT) SAE 90 mineral oil 85 Basic salt of Example 2 8 Neutral salt of Example 7 4 Dibutyl tetrasulfide 4 2,6-ditert-butyl-4-methylphenol "4 COMPOSITION G (LUBRICANT) SAE 10W30 mineral oil 85 Basic salt of Example 2 8 Neutral salt of Example 8 4 Zinc di-primary-pentyl phosphorodithioate 4 Poly(alkylmethacrylate) viscosity index improving agent COMPOSI'Ill'ON H (LUBRICANT) SAE 10W30 mineral oil Q. 75 Basic salt of Example 2 l Neutral salt of Example 9 Barium dinonyl phosphorodithioate 5 Acylated product obtained by the reaction at 150 C. of tetraethylene pentamine (1 equivalent) \With an alkenyl-substituted succinic .anhydride having 75 carbon atoms in the alkenyl-substituent (1 equivalent) 5 What is claimed is:

1. A basic mixture of alkaline earth metal salts of acidic phosphorized olefin polymers having molecular weights ranging from about 150 to about 48,000 and prepared by the reaction of a polymeric reactant selected from the class consisting of olefin polymers and chlorinated olefin polymers with a phosphorizing agent selected from the class consisting of phosphorus sulfides, phosphorus thiohalides, phosphorus oxyhalides, chlorine and a phosphorus trihalide, sulfur and a phosphorus trihalide, yellow phosphorus and a sulfur halide, yellow phosphorus and sulfur, and phosphorus .trihalides; said mixture being characterized by a metal ratio greater than 10 about 2.5 and comprising (A) from parts to 95 parts by weight of a said metal salt having a metal rat-i0 greater than 4 and (B) from 5 parts to 60 parts by weight of a said metal salt having a meta-l ratio less than 2.

2. The basic mixture of claim 1 characterized further in that the acidic phosphorized olefin polymers are acidic phosphosul furized olefin polymers.

3. The basic mixture oi claim 1 characterized further in that the acidic phosphorized olefin polymers are derived from the reaction of phosphorus pentasulfide with a polyisobutene having a molecular weight within the range from about 500 to 5000.

4. The basic mixture of claim 1 characterized further in that the alkaline earth metal salts are barium salts.

5. A basic mixture of barium salt of an acidic phos phosul'rturized olefin polymer having a molecular weight from about 500 to 5000, said mixture being characterized by a metal rat-i0 within the range from about 3 to about 7 and comprising (A) from parts to 90 parts by weight of a said barium salt having a metal ratio greater than 6 and prepared by carbonating a said acidic phosphosulfurized olefin polymer with an excess of barium oxide in the presence of a phenolic promoting agent, and (B) from 10 parts to 50 parts by weight of a said barium salt having a metal ratio less than 1.5.

6. The basic mixture of claim 5 characterized further in that the acidic phosphosulfurized olefin polymer is derived from the reaction of phosphorus pentasulfide with a polyisobutene having a molecular weight: of about 1000.

7. A basic mixture of barium salt of an acidic phosphosul-furized polyisobutene having a molecular Weight of about 1000, said mixture being characterized by a metal ratio of about 5 and comprising (A) about parts by Weight of said barium salt having a metal ratio of about 10 and prepared by .carbonating a said acid phosphosulfurized polyisobu-tene with at least 10 equivalents of barium oxide in the presence of a phenolic promoting agent and (B) about 40 parts by Weight of a said barium salt having a metal ratio of about 1.

8. A concentrate comprising from about 95 to about 20 parts by weight of tthe basic mixture of claim 1 and from about to about 5 parts by weight of a hydrocarbon oil.

9. A concentrate consisting essentially of from about to about 20 parts by Weight of the basic mixture of claim 7 and from about 80 to about 5 parts by Weight of a hydrocarbon oil.

10. A lubricating composition comprising a major proportion of a mineral lubricating oil and a minor proportion suificien-t to inhibit the formation of deposits of the basic mixture of claim 1.

11. A lubricating composition comprising from about '99 to about '80 parts by Weight of a mineral lubricating oil and from about 1 to about 20 parts by weight of the basic mixture of claim 7.

References Cited by the Examiner UNITED STATES PATENTS 2,316,088 4/1943 Loane et al. 252-32.7 2,606,872 8/ 1952 Gasser et al 25233 2,800,450 7/1957 Bondi et al. 25232.7 2,895,913 7/ 1959 Carlyle et al. 25233 2,906,709 9/1959 Lemmon et al. 25232.7 2,931,773 4/1960 Thompson et al. 252-33 2,943,052 6/1960 Carlyle et al. 25233 3,003,959 10/ 1961 Wilson et al. 25232.7

DANIEL E. WYMAN, Primary Examiner.

JULIUS GREENWALD, Examiner. 

1. A BASIC MIXTURE OF ALKALINE EARTH METAL SALTS OF ACIDIC PHOSPHORIZED OLEFIN POLYMERS HAVING MOLECULAR WEIGHTS RANGING FROM ABOUT 150 TO ABOUT 48,000 AND PREPARED BY THE REACTION OF A POLYMERIC REACTANT SELECTED FROM THE CLASS CONSISTING OF OLEFIN POLYMERS AND CHLORNATED OLEFIN POLYMERS WITH A PHOSPHORIZING AGENT SELECTED FROM THE CLASS CONSISTING OF PHOSPHORUS SULFIDES, PHOSPHORUS THIOHALIDES, PHOSPHORUS OXYHALIDES, CHLORINE AND A PHOSPHORUS TRIHALIDE, SULFRU AND PHOSPHORUS TRIHALIDE, YELLOW PHOSPHORUS AND A SULFUR HALIDE, YELLOW PHOSPHORUS AND SULFUR, AND PHOSPHORUS TRIHALIDES; SAID MIXTURE BEING CHARACTERIZED BY A METAL RATIO GREATER THAN ABOUT 2.5 AND COMPRISING (A) FROM 40 PARTS TO 95 PARTS BY WEIGHT OF A SAID METAL SALT HAVING A METAL RATIO GREATER THAN 4 AND (B) FROM 5 PARTS TO 60 PARTS BY WEIGHT OF A SAID METAL SALT HAVING A METAL RATIO LESS THAN
 2. 10. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND A MINOR PROPORTION SUFFICIENT TO INHIBIT THE FORMATION OF DEPOSITS OF THE BASIC MIXTURE OF CLAIM
 1. 